WO1997000934A1 - Aerosol cleaning compositions - Google Patents
Aerosol cleaning compositions Download PDFInfo
- Publication number
- WO1997000934A1 WO1997000934A1 PCT/AU1996/000373 AU9600373W WO9700934A1 WO 1997000934 A1 WO1997000934 A1 WO 1997000934A1 AU 9600373 W AU9600373 W AU 9600373W WO 9700934 A1 WO9700934 A1 WO 9700934A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cleaning composition
- composition according
- water
- group
- iso
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0043—For use with aerosol devices
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0031—Carpet, upholstery, fur or leather cleansers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/201—Monohydric alcohols linear
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/201—Monohydric alcohols linear
- C11D3/2013—Monohydric alcohols linear fatty or with at least 8 carbon atoms in the alkyl chain
Definitions
- This invention relates to cleaning compositions and in particular to compositions in aerosol form that are useful in cleaning a wide range of surface types including textiles such as clothing, fabrics and carpets and hard surfaces such as glass, metal, ceramics, porcelain, synthetic plastics and vitreous enamel.
- compositions for use in cleaning many surface types.
- these compositions may be divided into two groups, namely those that are solvent-based and those that are water-based. Both of these groups suffer from shortcomings which desirably should be overcome or at least improved.
- the present inventors have surprisingly found that one way of meeting this performance requirement for a water-based composition occurs when certain oil-in-water emulsions are formed. These emulsions are characterised by a substantial proportion or all of the aerosol propellant forming a part of the oil-phase when the composition is fully formulated. Disclosure of Invention
- the present invention consists in a cleaning composition comprising in aerosol form an oil-in-water emulsion containing:
- the boiling off of the propellant from the surface onto which a composition of the invention is discharged is characterised by a bubbling action on the surface. This bubbling action could also be described as
- the bubbling action is sustained, being generally characterised by an initial vigorous action for up to about 15 seconds then a continuous, less vigorous phase for up to 1 minute or more.
- compositions on discharge will be further characterised presenting as a wet spray in appearance. In this form the composition "wets out" the stain.
- the bubbling action contributes significantly to the broad spectrum cleaning performance of the compositions of the invention by providing a physical lifting action.
- the retained propellant is released in the form of bubbles which relatively quickly break releasing propellant to the atmosphere.
- the sustained nature of this bubbling action provides a prolonged cleaning action.
- compositions in the prior art do not display the sustained bubbling action on account of the propellant rapidly flashing off to the atmosphere.
- compositions of the present invention are water-based although it is evident that their cleaning performance is equivalent to or exceeds solvent-based compositions. This is indeed surprising in view of prior art water-based compositions. Nature of the Emulsion
- compositions of the invention a concentrate which includes (b), (c), (d) and (e) will be formed. Propellant is added to this concentrate to create compositions of the invention.
- the concentrate Prior to the addition of propellant.
- the concentrate desirably is a stable oil-in-water emulsion, preferably a substantially clear microemulsion.
- an oil-in-water emulsion is formed such that sufficient of the propellant is retained in the emulsion on discharge to a surface so that the retained propellant boils to create a bubbling action on the surface.
- Such an emulsion may be clear or characterised by a slight haziness through to a milky liquid to the presence of some separate oil layer.
- compositions of the invention ie when the propellant is added to the concentrate, it is preferred that substantially all of the propellant is taken up in the oil-phase to form an oil-in-water emulsion.
- This emulsion is desirably a stable clear microemulsion.
- Emulsions with some separate oil phase are acceptable providing that the separate oil phase portion re-emulsifies on shaking and sufficient of the propellant is retained in the emulsion on discharge to a surface such that the retained propellant boils to create a bubbling action on the surface, (a) Propellant
- hydrocarbon propellants are used in the compositions of the invention in a total amount from 2 to 60% w/w.
- hydrocarbon propellants that may be used are acetylene, methane, ethane, ethylene, propane, propene, n-butane, n-butene. iso-butane, iso-butene, pentane. pentene. iso-pentane and iso-pentene. Mixtures of these propellants may also be used.
- propellants typically contain a number of hydrocarbon gases.
- unodourised commercial butane available from Boral Gas
- propellants include propane, n-butane, iso-butane, pentane and iso-pentane. whilst most preferred are propane, n-butane and iso-butane.
- concentration of propellant will be from 2 to 60% w/w. generally the concentration will be from 5 to 50% w/w: preferably from 10 to 30%) w/w.
- the person skilled in the art will appreciate that the pressure in an aerosol package will be determined by the propellant or mixture of propellants. This pressure will have a determining effect on spray rate. Hence for any particular valve system, varying the propellant or propellant mixture will allow for the selection of a desired spray rate. Likewise, for a particular propellant or propellant mixture, it is possible to select a valve and actuator system to achieve a desired rate.
- One or more surfactants are included in a total amount of from 2 to 50%) w/w. preferably from 5 to 25% w/w. Either nonioiiic, amphoteric, anionic or cationic surfactants may be used, although nonionic and/or amphoteric surfactants are preferred.
- the surfactants function primarily in the formation of the emulsion. Desirably, the surfactants also contribute to cleaning.
- an individual surfactant component may be in a concentration as low as 0.1 to 0.5% w/w.
- sodium lauroyl sarcosinate may be used in a concentration of 0.2% w/w as a corrosion inhibitor.
- Surfadone LP300 in a concentration of 0.5% w/w may be used to improve wetting and stain removal. They will, however, participate in the oil-in-water emulsion.
- surfactants that may be used are as follows: Nonionic surfactants - sorbitan fatty acid ester ethoxylates. glycerol fatty acid ester ethoxylates.
- sorbitan fatty acid esters glycerol fatty acid esters, coconut monoethanolamide ethoxylates. tall oil ethoxylates, polypropylene glycol ethoxylates. fatty acid alkanolamides such as coconut mono- and diethanolamide. fatty alcohol ethoxylates and propoxylates. amine oxides, n- alkyl pyrrolidones. alkyl polysaccharides such as sucrose esters and alkyl polyglycosides, alkyl phenol ethoxylates. ethoxylated castor oil. fatty acid ethoxylates, fatty amine ethoxylates, polyglycerol fatty acid esters.
- Anionic surfactants sodium lauryl ether sulfate, triethanolamine lauryl sulphate, magnesium lauryl sulfate. sulfosuccinate esters, ammonium lauryl sulfate. alkyl sulfonates. sodium lauryl sulfate. sodium alpha olefin sulfonates. alkyl sulfates. sulfated alcohol ethoxylates. sulfated alkyl phenol ethoxylates. sodium xylene sulfonate.
- alkylbenzene sulphonates such as triethanolamine dodecylbenzene sulfonate, sodium dodecylbenzene sulfonate. calcium dodecylbenzene sulfonate. xylene sulfonic acid, dodecylbenzene sulfonic acid.
- N-alkoyl sarcosinates such as sodium lauroyl sarcosinate. dialkylsulfosuccinates, N-alkoyl sarcosines such as lauroyl sarcosine.
- Amphoteric surfactants - betaines, n-alkyl pyrrolidones because it has a resonance structure, it may behave as a zwitterionic substance), imidazolines.
- Cationic surfactants - quaternary ammonium compounds including alkyl dimethyl benzyl ammonium chloride, dialkyl dimethyl ammonium chloride, alkyl trimethyl ammonium chloride or bromide, salts of organic or inorganic acids with fatty amines and fatty amine ethoxylates.
- Mixtures of surfactants types may be used such as nonionic and anionic surfactants.
- a proprietary mixture of this type is Monamulse DL 1273 available from Mona Industries. Inc.
- Such a property is important to the performance of the compositions of the invention, since what is required is a bubbling action on the surface, rather than a foam.
- Preferred water immiscible organic compounds will usually have a secondary cleaning functionality through their solvency properties.
- One or more water immiscible organic compounds are included in the composition in a total amount from 0.1 to 30% w/w, preferably 0.5% to 30% w/w. most preferably 2% w/w to 20% w/w.
- silicone antifoams may be used such as Dow Corning Antifoam A.
- water immiscible organic compounds include - liquid n- paraffins.
- Isopar M and Isopar V (available from Exxon) naphthene-containing solvents - Exxsol D40. Exxsol D60. Exxsol D80. Nappar 10 (available from Exxon) ester solvents - such as alkyl acetates, examples being Exxate 1000.
- Exxate 1300 (available from Exxon), and Coasol (available from Chemoxy International).
- silicone solvents or oils - Dow Corning 244. 245. 344 and 345 fluids.
- terpenes - eucalyptus oil. cineole. orange oil.
- limonene fatty amines - soya amines, tallow amines, cocoamines.
- fatty acids - caprylic acid, caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid.
- Preferred water immiscible organic compounds are liquids at room temperature.
- Particularly preferred are hydrocarbon solvents, especially those that are good grease solvents.
- Most preferred are hydrocarbon solvents having a low solvent odour such as n-paraffins and iso-paraffins.
- One or more water miscible organic coupling agents are included in a total amount of from 0.5 to 40% w/w. preferably 5 to 30%) w/w.
- the coupling agent primarily functions to couple the propellant to the water and the water immiscible organic compound to the water. This assists in the formation of the emulsion and the retention of the propellant after discharge of compositions of the invention.
- the coupling agent also functions to couple the surfactant to the water, so as to prevent insolubility and/or gelling when it occurs.
- a secondary function is to provide some solvency for cleaning.
- the compounds that may be used are:- low molecular weight alcohols such as methanol. ethanol, n- propanol. iso-propanol.
- n-butanol and iso-butanol glycol ethers such as ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether and diethylene glycol monobutyl ether: glycols such as propylene glycol.
- hexylene glycol and ethylene glycol polyglycols such as PEG200 and PEG6000: polypropylene glycols: polyols such as glycerol.
- sorbitol. pentaerythritol and mannitol low molecular weight ketones such as acetone: and
- the water is included in the compositions of the invention in an amount of from 10 to 70%) w/w, preferably 25 to 55%) w/w.
- the water is purified before use and may be deionised or distilled.
- Surfactant additives may be included to enhance cleaning and washout performance.
- examples include good wetting agents, dispersing agents and the like. Specific examples include Surfadone LP 300 (n-dodecyl-2-pyrrolidone available from ISP) and Surfadone LP 100 (n-octyl-2-pyrrolidone) ; as good wetting agents, sodium lauryl ether sulphate as a dispersing agent for inorganic soil, (ii) Alkaline builder salts such as sodium carbonate, sodium sesquicarbonate, sodium tripolyphosphate, tetrasodium pyrophosphate, tetrapotassium pyrophospate. zeolites, sodium hexametaphosphate.
- Corrosion inhibitors such as sodium lauroyl sarcosinate, AMP regular, sodium nitrite, QAI 50% - 2 hydroxy propamine nitrite (available from Enviro Systems USA).
- Co-surfactants water immiscible coupling agents - including C H -C 1n alcohols.
- compositions of the invention which are toilet cleaners.
- Such compositions will usually require the use of synthetic plastic aerosol containers.
- Thickening agents particularly to retard release of propellant from the bubbling surface. May also be used for particular compositional requirements such as toilet cleaners to retain composition on angular surfaces.
- Abrasives particularly for hard surface cleaning compositions. An abrasive may be deposited from the composition and mechanically agitated to provide additional cleaning. Compounds such as fumed silica may be used.
- Alkaline compounds - partictilarly for hard surfaces and including ammonia, amines, such as mono-, di-, and triethanolamine. morpholine and AMP regular,
- Antimicrobials including disinfectant, antibacterial and germicidal compounds.
- Enzymes including protease, amylase, lipase and cellulase
- Chlorine, oxygen or reducing bleaching substances - such as hypochlorite.
- Such compositions will usually require the use of synthetic plastic aerosol containers.
- Supplementary propellants such as dimethyl ether and hydrofluorocarbons .
- the pH of the compositions is not critical and as mentioned previously, a toilet cleaning composition may have a very low pH, typically 1 or less. Similarly, some hard surface cleaning compositions may have a very high pH such as 13 or above. For other cleaning purposes, the pH may be in the range of from 7 up to 11.5.
- compositions of the invention may be prepared in the form of a variety of cleaning compositions including textile cleaners, such as carpet cleaners and prewash cleaners: hard surface cleaners for uses such as toilets, tiles, glass, stainless steel, ovens, kitchen, bathroom surfaces; paint strippers and mildew removers.
- compositions of the invention a concentrate is formed by dissolving the water phase ingredients and then adding the oil phase ingredients with stirring. In some circumstances heating may be required. This concentrate is then filled into aerosol packages and gassed with propellant in a conventional manner.
- EXAMPLES In order to better understand the nature of the invention, the . following examples, which illustrate prewash cleaning compositions, were prepared.
- the pH of this example was about 11 and pressure about 65-68 psi at 25 ( C.
- the pH of this example was about 11 and pressure about 65-68 psi at 25°C.
- the pH of this example was about 11 and pressure about 50-51 psi at 25 C.
- the pH of this example was about 11.5 and pressure about 65-68 psi at 25 C.
- Norpar 15 - Exxon (mixture of predominantly C ⁇ :) - C, 4 n-alkanes)
- Norpar 12 - Exxon (mixture of predominantly C, preparat - C ): , n-alkanes)
- Fabric swatches are to be washed according to washing conditions given above prior to staining.
- Standard time between staining and prewash application is 24 hours.
- Aerosols and Triggers apply pre-wash for 1 minute before washing.
- Stains are rated by n experienced people independently and the ratings averaged for each stain.
- Stains are rated in strong "south" daylight (would be north light in the northern hemisphere). White swatches are laid flat on a dark background for rating, this procedure makes rating easier and more reproducible, especially for oil stains.
- Aerosol valves of the same specification were used in both comparisons for R, S, Example 1 and Example 5. It was observed that the use of the integrated actuator/overcap delivered the composition faster to the surface as compared with the Delta actuator. This may mean that more propellant is retained with a subsequent more vigorous and longer lasting bubbling action. In addition to outstanding cleaning performance for a water-based prewash cleaning composition, the compositions of this invention display a number of advantages over the prior art:-
- compositions In assessing flamniability, preferred compositions exhibit no burn back and do not self sustain burning. By contrast prior art hydrocarbon solvent based compositions usually self sustain burning. Further, when hydrocarbon propellant is used in combination with hydrocarbon solvent, the compositions usually burn back as well.
- VOC's volatile organic compounds
- compositions a stable clear microemulsion of the hydrocarbon propellant is formed which obviates the need for shaking the aerosol before use.
- the bubbling action on the surface provides a visual indication to consumers of the cleaning action of the compositions.
- the bubbling action is achieved in the presence of surfactants in a water-based composition without creating a foam cover.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9609207A BR9609207A (en) | 1995-06-23 | 1996-06-21 | Aerosol cleaning composition and process for cleaning a surface and forming a cleaning composition |
EP96918509A EP0840779A4 (en) | 1995-06-23 | 1996-06-21 | Aerosol cleaning compositions |
AU61145/96A AU699687B2 (en) | 1995-06-23 | 1996-06-21 | Aerosol cleaning compositions |
CA002225445A CA2225445C (en) | 1995-06-23 | 1996-06-21 | Aerosol cleaning compositions |
NZ310358A NZ310358A (en) | 1995-06-23 | 1996-06-21 | Aerosol cleaning compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9512900.3A GB9512900D0 (en) | 1995-06-23 | 1995-06-23 | Improvements in or relating to organic compositions |
GB9512900.3 | 1995-06-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997000934A1 true WO1997000934A1 (en) | 1997-01-09 |
Family
ID=10776620
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AU1996/000373 WO1997000934A1 (en) | 1995-06-23 | 1996-06-21 | Aerosol cleaning compositions |
Country Status (12)
Country | Link |
---|---|
US (1) | US6150318A (en) |
EP (1) | EP0840779A4 (en) |
AR (1) | AR002580A1 (en) |
AU (1) | AU699687B2 (en) |
BR (1) | BR9609207A (en) |
CA (1) | CA2225445C (en) |
GB (1) | GB9512900D0 (en) |
MX (1) | MX9710281A (en) |
MY (1) | MY128097A (en) |
NZ (1) | NZ310358A (en) |
WO (1) | WO1997000934A1 (en) |
ZA (1) | ZA965286B (en) |
Cited By (14)
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WO1998004666A1 (en) * | 1996-07-29 | 1998-02-05 | The Clorox Company | Aerosol carpet cleaner |
EP0949324A1 (en) * | 1998-04-08 | 1999-10-13 | The Procter & Gamble Company | Carpet cleaning compositions and method for cleaning carpets |
WO1999066021A1 (en) * | 1998-06-12 | 1999-12-23 | Buck-Chemie Gmbh & Co. | Sanitising agent |
WO2000024854A1 (en) * | 1998-10-28 | 2000-05-04 | Reckitt Benckiser Inc | Alkaline carpet cleaning compositions |
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US6846793B1 (en) | 2003-03-19 | 2005-01-25 | Ecolab, Inc. | Cleaning concentrate |
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US6541435B2 (en) * | 2000-12-07 | 2003-04-01 | 3M Innovative Properties Company | Engine cleaner composition |
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- 1996-06-21 CA CA002225445A patent/CA2225445C/en not_active Expired - Lifetime
- 1996-06-21 BR BR9609207A patent/BR9609207A/en not_active IP Right Cessation
- 1996-06-21 AU AU61145/96A patent/AU699687B2/en not_active Expired
- 1996-06-21 WO PCT/AU1996/000373 patent/WO1997000934A1/en not_active Application Discontinuation
- 1996-06-21 ZA ZA9605286A patent/ZA965286B/en unknown
- 1996-06-21 NZ NZ310358A patent/NZ310358A/en unknown
- 1996-06-21 EP EP96918509A patent/EP0840779A4/en not_active Withdrawn
- 1996-06-24 US US08/669,584 patent/US6150318A/en not_active Expired - Lifetime
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Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998004666A1 (en) * | 1996-07-29 | 1998-02-05 | The Clorox Company | Aerosol carpet cleaner |
EP0949324A1 (en) * | 1998-04-08 | 1999-10-13 | The Procter & Gamble Company | Carpet cleaning compositions and method for cleaning carpets |
WO1999053005A1 (en) * | 1998-04-08 | 1999-10-21 | The Procter & Gamble Company | Carpet cleaning compositions and method for cleaning carpets |
WO1999066021A1 (en) * | 1998-06-12 | 1999-12-23 | Buck-Chemie Gmbh & Co. | Sanitising agent |
WO2000024854A1 (en) * | 1998-10-28 | 2000-05-04 | Reckitt Benckiser Inc | Alkaline carpet cleaning compositions |
US6693068B1 (en) | 1998-10-28 | 2004-02-17 | Reckitt Benckiser Inc. | Alkaline carpet cleaning composition comprising a pyrrolidone-based solvent |
WO2002097018A1 (en) * | 2001-05-30 | 2002-12-05 | Reckitt Benckiser Inc | Foam alkaline hard surface cleaner |
US7008911B2 (en) | 2002-09-06 | 2006-03-07 | Ecolab, Inc. | Non-surfactant solubilizing agent |
US6846793B1 (en) | 2003-03-19 | 2005-01-25 | Ecolab, Inc. | Cleaning concentrate |
DE10342289B3 (en) * | 2003-09-12 | 2005-06-23 | Detax Gmbh & Co. Kg | Use of a foam-forming composition comprising organic solvent, surfactant, foam stabilizer and water to clean hearing aids |
DE102004026684A1 (en) * | 2004-05-28 | 2005-12-29 | Stockhausen Gmbh | Skin cleansing preparations, in particular for removing printing inks and / or ink soils |
WO2007010449A1 (en) * | 2005-07-15 | 2007-01-25 | The Procter & Gamble Company | Self-pressurized spray stain remover |
US7307053B2 (en) | 2005-12-20 | 2007-12-11 | S.C. Johnson & Son, Inc. | Combination air sanitizer, soft surface deodorizer/sanitizer and hard surface disinfectant |
DE102006003336A1 (en) * | 2006-01-23 | 2007-07-26 | Henkel Kgaa | Sprayable all-purpose cleaner |
DE102006049673A1 (en) * | 2006-10-18 | 2008-04-24 | Henkel Kgaa | Hand dishwashing detergent with improved oil solubilization |
WO2014062532A1 (en) * | 2012-10-15 | 2014-04-24 | Ecolab Usa Inc. | Leather and/or vinyl cleaner and moisturizer and method of making same |
US9062282B2 (en) | 2012-10-15 | 2015-06-23 | Ecolab Usa Inc. | Leather and/or vinyl cleaner and moisturizer and method of making same |
US9719053B2 (en) | 2012-10-15 | 2017-08-01 | Ecolab Usa Inc. | Leather and/or vinyl cleaner and moisturizer and method of making same |
US10351801B2 (en) | 2012-10-15 | 2019-07-16 | Ecolab Usa Inc. | Leather and/or vinyl cleaner and moisturizer and method of making same |
Also Published As
Publication number | Publication date |
---|---|
AU699687B2 (en) | 1998-12-10 |
CA2225445C (en) | 2007-12-04 |
AR002580A1 (en) | 1998-03-25 |
EP0840779A1 (en) | 1998-05-13 |
ZA965286B (en) | 1997-02-17 |
GB9512900D0 (en) | 1995-08-23 |
NZ310358A (en) | 1999-11-29 |
EP0840779A4 (en) | 1999-09-22 |
MY128097A (en) | 2007-01-31 |
BR9609207A (en) | 1999-07-27 |
US6150318A (en) | 2000-11-21 |
MX9710281A (en) | 1998-08-30 |
CA2225445A1 (en) | 1997-01-09 |
AU6114596A (en) | 1997-01-22 |
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